EP2331584A1 - Composants catalyseurs pour la polymérisation d oléfines - Google Patents

Composants catalyseurs pour la polymérisation d oléfines

Info

Publication number
EP2331584A1
EP2331584A1 EP09783122A EP09783122A EP2331584A1 EP 2331584 A1 EP2331584 A1 EP 2331584A1 EP 09783122 A EP09783122 A EP 09783122A EP 09783122 A EP09783122 A EP 09783122A EP 2331584 A1 EP2331584 A1 EP 2331584A1
Authority
EP
European Patent Office
Prior art keywords
catalyst component
polymerization
prepolymerized
molar ratio
olefins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09783122A
Other languages
German (de)
English (en)
Other versions
EP2331584B1 (fr
Inventor
Gianni Collina
Anna Fait
Ofelia Fusco
Giampiero Morini
Lorella Pedriali
Rosa Spoto
Paolo Vincenzi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Poliolefine Italia SRL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Poliolefine Italia SRL filed Critical Basell Poliolefine Italia SRL
Priority to EP09783122A priority Critical patent/EP2331584B1/fr
Publication of EP2331584A1 publication Critical patent/EP2331584A1/fr
Application granted granted Critical
Publication of EP2331584B1 publication Critical patent/EP2331584B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium

Definitions

  • a pre-polymerized catalyst component for the polymerization of olefins CH 2 CHR, wherein R is hydrogen or a Ci-Ci 2 hydrocarbyl group, comprising a solid catalyst component characterized by comprising Mg, Ti halogen and an electron donor (ID) selected from the alkyl esters of aromatic dicarboxylic acids in such an amount that the a molar ratio
  • ID/Mg ranges from 0.025 to 0.065 and the Mg/Ti molar ratio is higher than 13, said solid catalyst component containing an amount of ethylene polymer up to 5Og per g of said solid catalyst component.
  • the ID/Mg molar ratio ranges from 0.030 to 0.055 and most preferably from 0.035 to 0.050.
  • the Mg/Ti molar ratio is higher than 14 and most preferably higher than 15. Especially it ranges from 15 to 30.
  • the amount of ethylene polymer ranges from 0.1 to 15g, more preferably said amount ranges from 0.5 to 5g and in particular from 0.5 to 3g per g of solid catalyst component.
  • the solid catalyst component in its non pre-polymerized form is also characterized by a porosity, measured by the mercury method, due to pores with radius equal to or lower than l ⁇ m, ranging from 0.45 cmVg to 1 cmVg, preferably from 0.5 cmVg to 0.9 cmVg and more preferably from 0.6 to 0.9 cmVg.
  • the electron donor compound (ID) is preferably selected from C1-C20 alkyl esters of phthalic acids, possibly substituted. Particularly preferred are the Ci-C ⁇ linear or branched alkyl esters.
  • diethyl phthalate di-n-propyl phthalate, di-n-butyl phthalate, di-n- pentyl phthalate, di-i-pentyl phthalate, bis(2-ethylhexyl) phthalate, ethyl-isobutyl phthalate, ethyl-n-butyl phthalate, di-n-hexyl phthalate, di-isobutylphthalate.
  • the Mg, Ti and halogen atoms preferably derive from a titanium compound having at least a Ti-halogen bond and an Mg halide.
  • the magnesium halide is preferably MgCl2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts.
  • Patents USP 4,298,718 and USP4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
  • the preferred titanium compounds used in the catalyst component of the present invention are selected among those of formula Ti(OR) n - y X y , where n is the valence of titanium, y is a number between 1 and n, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • TiCU and TiCU are the most preferred.
  • the preparation of the solid catalyst component can be carried out according to several methods.
  • the solid catalyst component can be prepared by reacting a titanium compound of the formula described above, preferably TiCU, with a magnesium chloride deriving from an adduct having formula MgCUpROH, where p is a number between
  • the adduct can be prepared in suitable spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 0 C).
  • the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles.
  • the desired average particle size is obtained by modulating the energy provided to the system by way of shear stresses. Generally speaking, smaller particles can be obtained by increasing the shear stress and therefore the extent of stirring in the stage of mixing the molten MgCU-alcohol adduct with the inert hydrocarbon.
  • the average size of the spherical particles of the adduct can vary from 5 to 100 ⁇ m while most commonly is in the range from 10 to 90 ⁇ m depending on the desired application of the final catalyst.
  • the particle size distribution (SPAN) of the adduct is generally lower than 1.5, calculated
  • P90 is the value of the diameter such that 90% of the total volume of particles have a diameter lower than that value
  • PlO is the value of the diameter such that 10% of the total volume of particles have a diameter lower than that value
  • P50 is the value of the diameter such that 50% of the total volume of particles have a diameter lower than that value.
  • the average particle size (APS) of the adduct particle, of the non prepolymerized catalyst component and of the prepolymerized catalyst component and their particle size distribution as well, are determined with the method described in the characterization section which is based on optical diffraction.
  • the adduct particles can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130 0 C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct particles (dealcoholated or as such) in cold TiCU (generally 0 0 C); the mixture is heated up to 80- 130 0 C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCU can be carried out one or more times and it is preferably carried out at least two times.
  • the electron donor compound can be added during the treatment with TiCU- It can be added together in the same treatment with TiCU or separately in two or more treatments. In any case the donor should be used in this stage in amount with respect to the MgCl 2 pROH, such as to have a ID/Mg ratio ranging from 0.08 to 0.14 and more preferably from 0.09 to 0.13.
  • the solid catalyst components obtained according to the above method show a surface area (by B. E. T. method) generally between 20 and 500 m 2 /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B. E. T. method) higher than 0.2 cmVg preferably between 0.2 and 0.6 cmVg.
  • the pre-polymerization can be carried out in liquid phase, (slurry or solution) or in gas-phase at temperatures generally lower than 50 0 C, preferably between -20 and 40 0 C and more preferably between -10 and 30 0 C.
  • a liquid diluent in particular selected from liquid hydrocarbons.
  • pentane, hexane and heptane are preferred.
  • the prepolymerized catalyst of the invention are further characterized by an apparent density ranging from 0.30 to 0.45 g/cm 3 preferably from 0.35 to 0.40 g/cm 3 measured as described in the characterization section.
  • the prepolymerized catalyst of the invention in addition to the very high activity also show an improved behavior in terms of handling expressed as very small amount of catalyst remaining in the drum after unloading.
  • Prepolymerized catalysts with apparent density are obtained by subjecting the solid catalyst components with the specific ID/Mg and Mg/Ti molar ratio can be obtained by operating under carefully controlled prepolymerization conditions in terms of reactor loading, temperature, aluminum alkyl concentration and stirring velocity.
  • operating at relatively low reactor loading, relatively high stirring velocity, at low aluminun alkyl and ethylene concentration for long reaction times avoids or minimizes the formation of aggregated particles which lower the apparent density.
  • the prepolymerized solid catalyst components according to the present invention are used in the polymerization of olefins by reacting them with organoaluminum compounds according to known methods.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
  • the use of the prepolymerized catalyst of the invention is particularly advantageous in fluidized-bed reactors not provided with an upstream prepolymerization section. Notwithstanding that, it allows obtaining polymers, in particular propylene polymers, with bulk densities higher than 0.43 g/cm 3 in conjunction with activities of about 20Kg/g of solid catalyst component.
  • the polymerization is generally carried out at temperature of from 40 to 120 0 C, preferably of from 40 to 100 0 C and more preferably from 50 to 90 0 C.
  • the polymerization is carried out in gas-phase the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In the bulk polymerization the operating pressure is generally between 1 and 8

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un composant catalyseur prépolymérisé pour la polymérisation d’oléfines CH2=CHR, où R est un hydrogène ou un groupe hydrocarbyle en C1-C12, comprenant un composant catalyseur solide caractérisé en ce qu’il comprend Mg, Ti, un halogène et un donneur d’électrons (ID) choisi parmi les esters d’alkyle d’acides dicarboxyliques aromatiques en une quantité telle que le rapport molaire ID/Mg soit dans la plage de 0,025 à 0,07 et le rapport molaire Mg/Ti soit supérieur à 13, ledit composant catalyseur prépolymérisé contenant une quantité de prépolymère d’éthylène allant jusqu’à 50 g par g dudit composant catalyseur solide.
EP09783122A 2008-09-26 2009-09-17 Composants catalytiques pour la polymérisation d'oléfines Not-in-force EP2331584B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09783122A EP2331584B1 (fr) 2008-09-26 2009-09-17 Composants catalytiques pour la polymérisation d'oléfines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08165213 2008-09-26
US19512908P 2008-10-03 2008-10-03
EP09783122A EP2331584B1 (fr) 2008-09-26 2009-09-17 Composants catalytiques pour la polymérisation d'oléfines
PCT/EP2009/062056 WO2010034664A1 (fr) 2008-09-26 2009-09-17 Composants catalyseurs pour la polymérisation d’oléfines

Publications (2)

Publication Number Publication Date
EP2331584A1 true EP2331584A1 (fr) 2011-06-15
EP2331584B1 EP2331584B1 (fr) 2012-11-21

Family

ID=41416073

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09783122A Not-in-force EP2331584B1 (fr) 2008-09-26 2009-09-17 Composants catalytiques pour la polymérisation d'oléfines

Country Status (9)

Country Link
US (1) US10125200B2 (fr)
EP (1) EP2331584B1 (fr)
JP (1) JP5140764B2 (fr)
KR (1) KR101599685B1 (fr)
CN (1) CN102164969B (fr)
BR (1) BRPI0919385B1 (fr)
ES (1) ES2399011T3 (fr)
RU (1) RU2493175C2 (fr)
WO (1) WO2010034664A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2583985A1 (fr) * 2011-10-19 2013-04-24 Basell Poliolefine Italia S.r.l. Composants de catalyseur pour la polymérisation des oléfines
EP2607387A1 (fr) * 2011-12-23 2013-06-26 Basell Poliolefine Italia S.r.l. Composants de catalyseur pré-polymérisés pour la polymérisation des oléfines
EP2607386A1 (fr) * 2011-12-23 2013-06-26 Basell Poliolefine Italia S.r.l. Composants de catalyseur pré-polymérisés pour la polymérisation des oléfines
CN109563191B (zh) * 2016-08-03 2021-03-19 住友化学株式会社 多相丙烯聚合材料的制造方法
CN116997578A (zh) 2021-04-16 2023-11-03 巴塞尔聚烯烃意大利有限公司 用于烯烃聚合的预聚合催化剂组分
KR20240058932A (ko) 2021-09-20 2024-05-07 다우 글로벌 테크놀로지스 엘엘씨 촉매-활성 예비중합체 조성물의 제조 방법 및 이에 의해서 제조된 조성물

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Also Published As

Publication number Publication date
BRPI0919385A2 (pt) 2016-01-19
US10125200B2 (en) 2018-11-13
EP2331584B1 (fr) 2012-11-21
RU2011116316A (ru) 2012-11-10
CN102164969A (zh) 2011-08-24
BRPI0919385B1 (pt) 2019-06-04
KR20110069120A (ko) 2011-06-22
CN102164969B (zh) 2015-11-25
ES2399011T3 (es) 2013-03-25
JP5140764B2 (ja) 2013-02-13
BRPI0919385A8 (pt) 2017-09-12
US20110251352A1 (en) 2011-10-13
KR101599685B1 (ko) 2016-03-04
JP2012503691A (ja) 2012-02-09
RU2493175C2 (ru) 2013-09-20
WO2010034664A1 (fr) 2010-04-01

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